CN108948313B - Environment-friendly artificial leather for automobile interior and manufacturing method thereof - Google Patents

Abstract

This article provides an eco-friendly artificial leather for automotive interiors and a method of making the same. The environmentally friendly product is manufactured using methods that are compatible with various environmental regulations, such as reducing greenhouse gas emissions. The artificial leather includes a bio-polyurethane-containing skin surface layer using a biomass-derived component extracted from a plant component, a solvent-free bio-polyurethane adhesive layer, and a biofiber base layer. These layers are stacked in sequence to minimize the use of organic solvents and components that are harmful to humans.

Description

Environmentally friendly artificial leather for car interior and method of making the same

technical field

The present invention relates to an environment-friendly artificial leather used in the interior of an automobile and a manufacturing method thereof. More particularly, the present invention relates to an eco-friendly artificial leather for automobile interiors that is configured to provide an eco-friendly product suitable for reducing greenhouse gas emissions and various environmental regulations. Manufacture of artificial leather such that a bio-polyurethane-containing skin surface layer, a solvent-free bio-polyurethane adhesive layer, and a bio-fiber base layer using a biomass-derived component extracted from a plant component are stacked in this order during the manufacturing method thereof Minimize the use of organic solvents and harmful components.

Background technique

A common method of manufacturing artificial leather includes forming a film on the surface of the epidermis by applying a polyurethane resin mixed solution synthesized using a petrochemical resource-based polyol and a chain extender in the presence of an organic solvent harmful to humans. In some cases, the method further includes applying dimethylformamide (DMF) and methyl ethyl ketone (MEK) to the release paper formed with various patterns, and drying the polyurethane resin mixture.

On the subsequently formed polyurethane film, a polyurethane adhesive synthesized from a petrochemical raw material containing an organic solvent is applied, whereby a cross-linking reaction is performed, and then a method of laminating the polyurethane film with a common fiber substrate is used to impart appropriate adhesive characteristics. The method of making artificial leather and the adhesive layer disposed on the intermediate layer of the product involves the use of large amounts of organic solvents (eg DMF and MEK). A separate drying process can be performed to minimize the residual amount of organic solvent, but it is difficult to completely remove the residual organic solvent.

Since the artificial leather in the prior art utilizes raw materials derived from petrochemical resources, such artificial leather has the disadvantage that it is difficult to actively comply with international environmental regulations, such as reduction of greenhouse gas emissions and harmfulness to human body while remaining in the environment reduction of emissions components.

Methods to reduce the amount of organic solvents are currently being developed, for example, studies involving the replacement of organic solvents with water-based polyurethanes or 100% solids solvent-free polyurethanes have been carried out. Research and development of artificial leather for automobile interiors using biomass-derived raw materials and applications are being started.

Korean Patent No. 10-0389934 discloses a method of treating an artificial leather product manufactured by using an aqueous polyurethane material of an aqueous polyurethane-based adhesive instead of the polyurethane containing an organic solvent in the related art. However, the aqueous polyurethane-based adhesive has the disadvantage that it is difficult to adjust the molecular weight during the synthesis of the adhesive, and due to limited synthetic raw materials, hydrolysis resistance, adhesive strength, durability, and the like are weak. In addition, about 50% to 60% moisture is contained in the adhesive raw material, wherein the energy cost becomes excessive when the adhesive raw material is dried, and it is difficult to laminate the adhesive raw material with the fibrous substrate. Adjust the appropriate stickiness characteristics.

Therefore, the prior art methods have drawbacks in terms of production stability, product reproducibility and bond strength. For example, the methods of the prior art are significantly deficient compared to methods using polyurethane adhesives containing organic solvents. Furthermore, it is not desirable to utilize prior art methods to reduce greenhouse gas emissions due to the utilization of feedstocks derived from petrochemical resources.

The information disclosed in this Background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

SUMMARY OF THE INVENTION

In order to solve the above problems, this paper provides environmentally friendly artificial leathers that can be manufactured according to the methods described herein. Compared to prior art methods, the manufacturing method described below provides a reduction in greenhouse gas emissions and is compliant with various environmental regulations. The artificial leather includes a bio-polyurethane-containing skin surface layer using a biomass-derived component extracted from a plant component, a solvent-free bio-polyurethane adhesive layer, and a bio-fiber base layer, which are stacked in this order. This minimizes the use of organic solvents and components that are harmful to humans.

Accordingly, various aspects of the present invention aim to provide environmentally friendly artificial leather that can be placed in the interior of an automobile.

Various aspects of the present invention aim to provide a method for manufacturing an eco-friendly artificial leather that can be placed in an automobile interior.

Various aspects of the present invention are directed to providing an environmentally friendly artificial leather for an automobile interior, the environmentally friendly artificial leather for an automobile interior comprising a skin surface layer comprising a bio-polyurethane stacked in sequence; a solvent-free bio-polyurethane adhesive layer; Biofiber basal layer. The solvent-free bio-urethane adhesive layer includes a hydroxyl-terminated polyurethane prepolymer prepared by polymerizing 2 to 5 parts by weight of an isocyanate-based compound with 100 parts by weight of a polyol mixture. The polyol mixture comprises: (1) a carbonate polyol having a functionality of 2 or greater and a number average molecular weight of 500 to 3,000, (2) a derivative having a curing temperature of 18°C to 55°C and a number average molecular weight of 1,000 to 3,000 A crystalline ester polyol from biomass, and (3) a chain extender derived from biomass having a functionality of 3 or greater and a number average molecular weight of 50 to 500. The biofiber base layer comprises a composite spun fiber comprising a polymer resin and a biomass-derived polytrimethylene terephthalate, wherein the polymer resin is selected from the group consisting of polyethylene terephthalate, polyacrylate, copolyparaphenylene Ethylene glycol dicarboxylate and polylactide were mixed with biomass-derived polytrimethylene terephthalate in a weight ratio of 1:1.

Various aspects of the present invention relate to methods for making eco-friendly artificial leather for automotive interiors. The method includes (a) forming a bio-polyurethane skin surface layer on a release paper; (b) forming a solvent-free bio-polyurethane adhesive layer by applying a solvent-free bio-polyurethane composition to the bio-polyurethane skin surface layer; and (c) ) forming a biofiber base layer on a solvent-free bio-polyurethane adhesive layer, wherein the solvent-free bio-polyurethane adhesive composition comprises by combining 2 to 5 parts by weight of an isocyanate-based compound with 100 parts by weight of a polyol Hydroxy-terminated polyurethane prepolymer prepared by polymerizing a mixture comprising (1) a carbonate polyol having a functionality of 2 or more and a number average molecular weight of 500 to 3,000, and (2) a curing temperature of 18°C a biomass-derived crystalline ester polyol having a number average molecular weight of 1,000 to 3,000 to 55°C, and (3) a biomass-derived chain extender having a functionality of 3 or greater and a number average molecular weight of 50 to 500, and The biofiber base layer includes composite spun fibers comprising a polymer resin and biomass-derived polytrimethylene terephthalate. The polymer resin is selected from polyethylene terephthalate, polyacrylate, copolyethylene terephthalate and polylactide. The polymer resin was mixed with biomass-derived polytrimethylene terephthalate in a 1:1 weight ratio.

The eco-friendly artificial leather for an automobile interior according to an exemplary embodiment of the present invention may be manufactured according to a method suitable for reducing greenhouse gas emissions and various environmental regulations. The method includes sequentially stacking a bio-polyurethane-containing skin surface layer using a biomass-derived component extracted from a plant component, a solvent-free bio-polyurethane adhesive layer, and a biofiber base layer to produce artificial leather. The advantage of the method is the minimization of the use of organic solvents and components harmful to the human body.

It is also possible to use eco-friendly products in the interior of automobiles that require high durability performance. In some embodiments, the vehicle is an environmentally friendly vehicle, such as, but not limited to, hydrogen vehicles, electric vehicles, and hybrid vehicles.

Other aspects and exemplary embodiments of the invention are discussed below.

It should be understood that the terms "vehicle" or "vehicle" or other similar terms as used herein generally include motor vehicles, including sport utility vehicles (SUVs), buses, trucks, passenger cars of various commercial vehicles, including Various boats, marine vessels, aircraft, etc., and includes hybrid vehicles, electric vehicles, pluggable hybrid electric vehicles, hydrogen-powered vehicles, and other alternative fuel vehicles (eg, fuels derived from energy sources other than petroleum). As mentioned herein, a hybrid vehicle is a vehicle having two or more power sources, such as both gasoline-powered and electric-powered vehicles.

The methods and apparatus of the present invention have other features and advantages that will be apparent from or more elucidated in the accompanying drawings, which are incorporated herein and which together with the detailed description serve to explain certain principles of the invention.

Description of drawings

FIG. 1 is a schematic diagram illustrating a method of manufacturing artificial leather according to an exemplary embodiment of the present invention.

2 is a photograph of observing a cross section of the artificial leather produced in Example 9 of the present invention by a scanning electron microscope (SEM).

FIG. 3 is a schematic diagram of a vehicle seat using artificial leather according to an exemplary embodiment of the present invention.

It should be understood that the appended drawings are not necessarily to scale, presenting a somewhat simplified representation of various features of the basic principles of the invention. The specific design features of the invention disclosed herein, including, for example, the specific dimensions, orientations, locations, and shapes, will be determined in part by the specific intended application and use environment.

In the figures, reference numbers refer to the same or equivalent parts of the invention throughout the several figures of the drawing.

Detailed ways

Reference will now be made in detail to various embodiments of the present invention, examples of which are illustrated in the accompanying drawings and described below. While the invention will be described in conjunction with exemplary embodiments, it should be understood that this description is not intended to limit the invention to those exemplary embodiments. On the contrary, the invention is intended to cover not only the exemplary embodiments, but also various alternatives, modifications, equivalents and others, which may be included within the spirit and scope of the invention as defined by the appended claims implementation plan.

Hereinafter, the present invention will be described in more detail by way of exemplary embodiments.

The environment-friendly artificial leather for automobile interior of the present invention has a leather surface layer 100 containing bio-polyurethane; a solvent-free bio-polyurethane adhesive layer 200 ; and a biofiber base layer 300 , which are stacked in sequence. The solvent-free bio-urethane adhesive layer 200 includes a hydroxyl-terminated polyurethane prepolymer prepared by polymerizing 2 to 5 parts by weight of an isocyanate-based compound with 100 parts by weight of a polyol mixture including (1) carbonate polyols having a functionality of 2 or more and a number average molecular weight of 500 to 3,000, (2) biomass-derived crystalline esters having a curing temperature of 18°C to 55°C and a number average molecular weight of 1,000 to 3,000 A polyol, and (3) a biomass-derived chain extender having a functionality of 3 or greater and a number average molecular weight of 50 to 500. And, the biofiber base layer 300 includes a composite spun fiber composed of a composite spun filament comprising a polymer resin and a biomass-derived polytrimethylene terephthalate. The polymer resin is selected from polyethylene terephthalate, polyacrylate, copolyethylene terephthalate and polylactide. And, the polymer resin was mixed with biomass-derived polytrimethylene terephthalate in a weight ratio of 1:1.

In an exemplary embodiment of the present invention, the term "biomass" refers to a bioalcohol-based polymer polymeric feedstock synthesized from sugars extracted from the cellulose of one or more renewable plant components, the renewable The plant component is selected from woody plant resources including corn, wheat, soybean and sugar cane.

In an exemplary embodiment of the present invention, the term "green carbon (C ₁₄ )" refers to an isotope of carbon present in biomass extracted from plant components as an indicator for reducing greenhouse gas emissions. Green carbon (C ₁₄ ) is a substance that is present in trace amounts in all living things, and due to its unstable nature, decays over time and eventually disappears. The presence of green carbon (C ₁₄ ) content indicates that green carbon (C ₁₄ ) is a substance derived from living organisms, and carbon is not present in an object synthesized from raw materials extracted from petroleum. For this reason, evidence of the existence of green carbon (C ₁₄ ) is a very important factor as a measure of an environmentally friendly material.

Hereinafter, each constituent component of the eco-friendly artificial leather according to the exemplary embodiment of the present invention will be described in detail.

(a) Skin surface layer 100 comprising bio-polyurethane

The polyurethane of the skin surface used in the exemplary embodiment of the present invention may use a bio-urethane resin obtained by subjecting a polyol mixture to an addition reaction, the polyol mixture containing polycarbonate polyol as a main raw material and containing About 5 to 15 wt% (eg, about 5 wt%, 6, 7, 8, 9, 10, 11, 12, 13, 14, or about 15 wt%) of the biomass-derived ester polyol and about 1 to 5 % by weight (eg, about 1, 2, 3, 4, or about 5 wt%) of chain extenders with aliphatic or cycloaliphatic polyisocyanates, such as hexamethylene diisocyanate (HDI), isophorone Diisocyanate (IPDI) and dicyclohexylmethane diisocyanate (H ₁₂ MDI). The skin surface layer 100 comprising the bio-polyurethane may have 5 to 15 wt% (eg, about 5 wt%, about 6 wt%, about 7 wt%, about 8 wt%, about 9 wt%, about 10 wt%, about 11 wt% %, about 12%, about 13%, about 14%, or about 15% by weight) content of green carbon ( _C14 ).

(b) Solvent-free bio-urethane adhesive layer 200

The solvent-free bio-polyurethane adhesive layer 200 in the exemplary embodiment of the present invention may include about 10 to 30 parts by weight (eg, about 10 parts by weight, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, or about 30 parts by weight) of an isocyanate-based compound and about 0.01 to 5 parts by weight (eg, about 0.01 parts by weight, about 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3 , 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9 , or about 5 parts by weight) of the curing catalyst. The solvent-free bio-urethane adhesive layer 200 may have about 15 to 35% (eg, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, or about 35% %) of green carbon (C ₁₄ ).

When preparing the solvent-free bio-urethane adhesive, the bio-polyurethane adhesive layer in which the micropores are formed can be prepared by further including nitrogen gas as a non-reactive gas at about 0.01 to 3 L/min (for example, about 0.01 L/min, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1, 1.2, 1.5, 1.8, 2, 2.2, 2.5, 2.8, or about 3 L/min) into a high speed stirrer while stirring the reaction mixture to form. The microporous solvent-free bio-polyurethane adhesive layer 200 can be produced at a temperature of preferably about 0.1 to 0.5 L/min (eg, about 0.21, 0.22, 0.23, 0.24, 0.24, 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.34, 0.35, 0.36, 0.37, 0.38, 0.39, 0.4, 0.41, 0.42, 0.43, 0.44, 0.44, 0.45, 0.46, 0.47, 0.48, 0.49, or about 0.5 L/min), more preferably 0.12 L/min while injecting nitrogen gas.

(b-1) Hydroxy-terminated polyurethane prepolymer

The term "hydroxyl-terminated polyurethane prepolymer" as used in the exemplary embodiment of the present invention refers to a content of about 1 to 3 wt % (eg, about 1 wt %, about 2 wt %) based on the total content of the polyurethane prepolymer % or about 3% by weight) of hydroxyl groups (-OH groups) in the form of residual hydroxyl groups at both ends of the polyurethane prepolymer that have not reacted with isocyanates.

The hydroxyl terminated polyurethane prepolymer of the present invention can be polymerized by polymerizing about 2 parts by weight to 5 parts by weight (eg, about 2, about 3, about 4, or about 5 parts by weight) of the isocyanate-based compound with 100 parts by weight of the polyol mixture To prepare, the polyol mixture includes a carbonate polyol having a functionality of 2 or greater and a number average molecular weight of 500 to 3,000, a biomass-derived curing temperature of 18°C to 55°C and a number average molecular weight of 1,000 to 3,000 crystalline ester polyols, and biomass-derived chain extenders having a functionality of 3 or greater and a number average molecular weight of 50 to 500.

The polyol mixture can include about 65 to 80 wt% (eg, about 65 wt%, about 66 wt%, about 67 wt%, about 68 wt%, about 69 wt%, about 70 wt%, about 71 wt%, about 72%, about 73%, about 74%, about 75%, about 76%, about 77%, about 78%, about 79%, or about 80% by weight) carbonate polyols , about 18 to 26 wt% (eg, about 18 wt%, about 19 wt%, about 20 wt%, about 21 wt%, about 22 wt%, about 23 wt%, about 24 wt%, about 25 wt%, or about 26 wt%) of crystalline ester polyols derived from biomass, and about 2 to 9 wt% (eg, about 2 wt%, about 3 wt%, about 4 wt%, about 5 wt%, about 6 wt%, about 7 wt %, about 8 wt %, or about 9 wt %) of the biomass-derived chain extender. The ester polyol may be used in an amount of about 18 to 26% by weight, based on the total weight of the polyol mixture (eg, about 18% by weight, about 19% by weight, about 20% by weight, about 21% by weight, about 22% by weight, about 23 wt %, about 24 wt %, about 25 wt % or about 26 wt %), when its content is less than 18 wt %, there is a problem of reduced green carbon content, and when its content is more than 26 wt %, there is hydrolysis resistance deteriorating problem. By adjusting the components of the polyol mixture in the proper proportions as described above, rigidity and strong cohesion can be exhibited while having a suitable specific melting temperature and viscosity.

As the carbonate polyol, a carbonate polyol having a functionality of 2 or more and a number average molecular weight of 500 to 3,000 can be used. Specifically, carbonate polyols can be prepared by one or more selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and cyclic It is synthesized by transesterification and condensation reaction of a hydroxyl compound of hexanediol with one or more ester compounds selected from the group consisting of alkylene carbonate, diaryl carbonate and dialkyl carbonate. Polyurethanes synthesized using carbonate polyols exhibit excellent properties in chemical resistance, hydrolysis resistance, weather resistance, and heat resistance, and thus can be used as main raw materials for polyurethanes with high durability.

Biomass-derived crystalline ester polyols with number average molecular weights of 1,000 to 3,000 can be prepared by one or more compounds selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,4-butanediol, and 1,6-hexanediol. Synthesized by polycondensation of diols with one or more acids selected from adipic acid (AA), sebacic acid (SA) and terephthalic acid, the diols being derived from corn as a biomass feedstock component Extracted and produced. Polyurethanes synthesized using biomass-derived polyols are excellent in elasticity, resilience, dimensional stability, cold resistance, and flexibility, and thus can be used as main raw materials for carbon dioxide-reducing environmentally friendly polyurethanes.

The biomass-derived chain extender having a number average molecular weight of 50 to 500 may be selected from the group consisting of 1,3-propanediol, ethylene glycol, 1,2-propanediol, 1,4-butanediol, 1,6-hexanediol , one or more of methylpentanediol and diethylene glycol extracted from corn as a biomass feedstock component of the feedstock. Chain extenders can be used to design polyurethane structures with excellent stiffness by increasing the degree of cross-linking cure.

Isocyanate-based compounds are isocyanates used for synthesizing hydroxyl-terminated polyurethane prepolymers, and can be selected from hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), dicyclohexylmethane diisocyanate (H ₁₂ MDI) ), one or more of xylene diisocyanate (XDI) and 4,4-diphenylmethane diisocyanate (MDI).

When the cushioning (filling feeling) of artificial leather is to be improved, based on 100 parts by weight of the hydroxyl-terminated polyurethane prepolymer, about 5 to 20 parts by weight (for example, about 5, about 6, about 7, about 8, about 9, about 10, about 11, about 12, about 13, about 14, about 15, about 16, about 17, about 18, about 19, or about 20 parts by weight) of inorganic filler. As the kind of inorganic filler, one or more fillers having an average diameter of about 1 μm or less and selected from calcium carbonate, aluminum hydroxide, alumina, magnesium oxide, talc, and silica can be used, but inorganic fillers are not limited to this.

Hydroxy-terminated polyurethane prepolymers exist as crystalline solids at room temperature, but can be melted at 60°C or lower by further reacting the polyol mixture with an isocyanate-based compound, and can be 100% synthesized from biomass-derived feedstocks Solid reactants that are designed to form rigid polyurethane bonds and improve production stability, reproducibility, etc., while exhibiting suitable viscosity.

The hydroxyl-terminated polyurethane prepolymer may have a melt viscosity at 60° C. of 2,000 to 8,000 cPs, and may have about 1 to 3 wt. % (eg, about 1 wt. 2 wt % or about 3 wt %) hydroxyl content. The hydroxyl terminated polyurethane prepolymer may have a melt viscosity at 60°C of 3,500 to 6,500 cPs. If the melt viscosity at 60° C. is less than 2,000 cPs, it is difficult to adjust a uniform thickness, and a slow cross-linking curing reaction deteriorates all physical properties, so this is not preferable. In contrast, if the melt viscosity at 60°C exceeds 8,000 cPs, there is a problem of limitation in uniformly mixing the hydroxyl-terminated polyurethane prepolymer in a high-speed reaction molding machine, and thus the production stability decreases. In consideration of production stability, production efficiency, gel time, reactivity, etc., the hydroxyl-terminated polyurethane prepolymer is heated at 40 to 70°C (for example, about 40°C, about 41°C, about 42°C, about 43°C, about 44°C) ℃, about 45℃, about 46℃, about 47℃, about 48℃, about 49℃, about 50℃, about 50℃, about 51℃, about 52℃, about 53℃, about 54℃, about 55℃, about 56°C, about 57°C, about 58°C, about 59°C, about 60°C, about 61°C, about 62°C, about 63°C, about 64°C, about 65°C, about 66°C, about 67°C, about 68°C C, about 69 C, or about 70 C) are effective for melting and reacting.

When the melting temperature of the hydroxyl-terminated polyurethane prepolymer is lower than 40°C, it takes a long time to melt the prepolymer. On the contrary, when the prepolymer has a melting temperature lower than 70°C, the cross-linking occurs due to the high temperature of the polyurethane reaction solution. and curing reactions occur rapidly during the coating process, where the gel time may become too short. Therefore, it is difficult to obtain uniform coating, and as a result, since the non-uniform solvent-free bio-urethane adhesive layer 200 is formed, there is a problem that the uniformity of the product is deteriorated.

(b-2) Isocyanate-based crosslinking agent compound

As the isocyanate-based crosslinking agent compound used as the crosslinking agent of the hydroxyl-terminated polyurethane prepolymer, an isocyanate-terminated prepolymer, carbodiimide-modified MDI, burette type HDI, isocyanurate HDI, etc. can be used , alone or in a mixture of two or more thereof, which can react with the active hydrogens of the hydroxyl groups in the molecular structure of low molecular weight polyols and isocyanates as reactants.

The isocyanate-based compound may be used in an amount of about 1.05 to 2.5 equivalents (eg, about 1.05, 1.06, 1.07, 1.08, 1.09, 1.20, 1.21, 1.22, 1.23, 1.24, 1.25, 1.26,1.27,1.28,1.29,1.30,1.31,1.32,1.33,1.34,1.35,1.36,1.37,1.38,1.39,1.4,1.41,1.42,1.43,1.44,1.45,1.46,1.47,1.48,1.49,1.5, 1.51,1.52,1.53,1.54,1.55,1.56,1.57,1.58,1.59,1.6,1.61,1.62,1.63,1.64,1.65,1.66,1.67,1.68,1.69,1.7,1.71,1.72,1.73,1.74,1.75, 1.76, 1.77, 1.78, 1.79, 1.8, 1.81, 1.82, 1.83, 1.84, 1.85, 1.86, 1.87, 1.88, 1.89, 1.9, 1.91, 1.92, 1.93, 1.94, 1.95, 1.96, 1.97, 1.98, 1.99, 2.0, 2.01, 2.02, 2.03, 2.04, 2.05, 2.06, 2.07, 2.08, 2.09, 2.1, 2.11, 2.12, 2.13, 2.14, 2.15, 2.16, 2.17, 2.18, 2.19, 2.2, 2.21, 2.22, 2.23, 2.24, 2.25, 2.26,2.27,2.28,2.29,2.3,2.31,2.32,2.33,2.34,2.35,2.36,2.37,2.38,2.39,2.4,2.41,2.42,2.43,2.44,2.45,2.46,2.47,2.48,2.49, or about 2.5 equivalents). Based on 1 equivalent of hydroxyl-terminated polyurethane prepolymer, when its content is less than 1.05 equivalents, the degree of crosslinking and curing is insufficient, resulting in poor adhesive strength and all physical properties, and when its content exceeds 2.5 equivalents, the remaining unreacted The larger amount of the isocyanate is such that problems such as hydrolysis resistance, chemical resistance, adhesive strength, etc. may be deteriorated while the product uniformity may be deteriorated.

(b-3) Curing catalyst

As the curing catalyst for urethaneization, publicly known curing catalysts can be used without particular limitation. For example, the curing catalyst is triethylamine (trade name: Dabco 33LV), bis(dimethylamino ether) (trade name: Dabco BL-11), N,N-dimethylcyclohexylamine (Polycat-8), Tris-dimethylaminopropylamine (Polycat-9), n-butyltin diacetate, 1,8-bicyclo(5,4,0)undecane (DBU), DBU-octanoate, etc. These curing catalysts can be used alone or used in combination.

(c) Biofiber base layer 300

The biofiber base layer 300 used in the exemplary embodiment of the present invention may comprise about 30 to 50 wt % (eg, about 30 wt %, about 31 wt %, about 32 wt %, about 33 wt %, about 34 wt %) wt%, about 35 wt%, about 36 wt%, about 37 wt%, about 38 wt%, about 39 wt%, about 40 wt%, about 41 wt%, about 42 wt%, about 44 wt%, about 45 wt% wt %, about 46 wt %, about 47 wt %, about 48 wt %, about 49 wt %, or about 50 wt %) composite spun fibers, about 25 to 35 wt % (eg, about 25 wt %, about 26 wt %) %, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33%, about 34%, or about 35% by weight) nylon fibers , and about 25 to 35% by weight (e.g., about 25%, about 26%, about 27%, about 28%, about 29%, about 30%, about 31%, about 32%, about 33 wt %, about 34 wt % or about 35 wt %) of a non-woven fabric layer of polyester fibers, or consisting of a reinforcement comprising a biomass-derived polytrimethylene terephthalate formed on the non-woven fabric layer Layers of composite nonwoven fabric layers.

As the biomass-derived polytrimethylene terephthalate, biomass-derived polytrimethylene terephthalate obtained by polycondensation of biomass-derived 1,3-propylene glycol and terephthalic acid can be used.

Composite spun fibers may include composite spun filament yarns, which will be selected from polyethylene terephthalate (PET), polyacrylate (PA), copolyethylene terephthalate (co-PET) ) and a polymer resin of polylactide (PLA) mixed with biomass-derived polytrimethylene terephthalate (PTT) in a weight ratio of 1:1. More specifically, the composite spun fibers may be bio-PPT/PET composite spun filament yarns or islands-in-the-sea or split long yarns comprising one or more selected from PTT/PA, PTT/Co-PET, and PTT/PLA. silk yarn. The composite spun fibers can have 2 to 3 denier (eg, about 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, or about 3 denier) and about 40 to 60 mm (eg, about 40 mm, 41 , 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59 or about 60 mm).

The nonwoven fabric layer may comprise a nonwoven fabric, which will have 1 to 2.5 denier (eg, about 1 denier, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4 , 2.5 denier) and an average fiber length of 40 to 60 mm (e.g., about 57, 58, 59 or about 60 mm) nylon chopped fibers and polyester fibers mixed with composite spun fibers. Since nylon fibers have high elasticity and good sound absorption properties, and polyester fibers have excellent thermal shrinkage properties, the fiber base density is increased, wherein cushioning and texture are improved.

The composite nonwoven layer may be constructed in a form in which a reinforcement layer comprising a reinforcement fabric comprising a biomass-derived polytrimethylene terephthalate is stacked on the nonwoven fabric layer. When the above-mentioned reinforcing layer is additionally further formed, better sensitivity and stretchability improvement can be expected during the processing of artificial leather.

The biofiber base layer 300 may have a basis weight of about ²⁰⁰ to 300 g/m (eg, about 270, 275, 280, 285, 290, 295, or about 300 g/m ² ) and in an amount of 1 to 20 wt % (eg, about 1 wt %, about 2 wt %, about 3 wt %, about 4 wt %, about 5%, about 6%, about 7%, about 8%, about 9%, about 10%, about 11%, about 12%, about 13%, about 14%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, about 19 wt%, or about 20 wt%) of green carbon ( _C14 ). At present, when the weight per unit area is less than 200 g/m ² , the density is too low so that the adhesive is absorbed in the fabric material in a large amount, therefore, the quality and sensitivity may be deteriorated, and when the weight per unit area exceeds 300 g/m ² , the non- Woven fabrics are too stiff to achieve excellent elasticity and soft texture.

In some aspects of the present invention, the method of manufacturing an eco-friendly artificial leather for automobile interiors of the present invention comprises: (a) forming a bio-polyurethane skin surface layer on a release paper; (b) by mixing a solvent-free bio-polyurethane composition Applying to the bio-polyurethane skin surface layer to form a solvent-free bio-polyurethane adhesive layer 200; and (c) forming a bio-fiber base layer 300 on the solvent-free bio-polyurethane adhesive layer 200, wherein the solvent-free bio-polyurethane adhesive The agent composition includes a hydroxyl-terminated polyurethane pre-polymer prepared by polymerizing about 2 parts by weight to 5 parts by weight (eg, about 2, 3, 4, or about 5 parts by weight) of an isocyanate-based compound and 100 parts by weight of a polyol mixture. polymers, the polyol mixture includes a carbonate polyol having a functionality of 2 or greater and a number average molecular weight of 500 to 3,000, and a curing temperature of about 18°C to 55°C (eg, about 18°C, about 19°C, about 20°C, about 21°C, about 22°C, about 23°C, about 24°C, about 25°C, about 26°C, about 27°C, about 28°C, about 29°C, about 30°C, about 31°C, about 32°C ℃, about 33℃, about 34℃, about 35℃, about 36℃, about 37℃, about 38℃, about 39℃, about 40℃, about 41℃, about 42℃, about 43℃, about 44℃, about 45°C, about 46°C, about 47°C, about 48°C, about 49°C, about 50°C, about 51°C, about 52°C, about 53°C, about 54°C, or about 55°C) and the number average molecular weight is 1,000 to 3,000 biomass-derived crystalline ester polyols, and biomass-derived chain extenders having a functionality of 3 or more and a number average molecular weight of 50 to 500, and the biofiber base layer 300 includes a composite spun Fibers, wherein a polymer resin selected from the group consisting of polyethylene terephthalate, polyacrylate, copolyethylene terephthalate and polylactide and polytrimethylene terephthalate derived from biomass Mix in a weight ratio of 1:1.

Step (b) may further comprise adding nitrogen gas as a non-reactive gas at about 0.01 to 3 L/min (eg, about 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2 L /min) into a high-speed mixer to prepare a solvent-free bio-polyurethane adhesive layer 200 having micropores formed therein.

Therefore, the eco-friendly artificial leather for automobile interior according to the exemplary embodiment of the present invention is formed by sequentially stacking the bio-polyurethane-containing skin surface layer 100 using the biomass-derived component extracted from the plant component, the solvent-free bio-polyurethane The adhesive layer 200, and the biofiber base layer 300 are used to minimize the use of organic solvents and components harmful to human body, thereby making it possible to manufacture environmentally friendly products suitable for reducing greenhouse gas emissions and various environmental regulations.

The eco-friendly product can also be used as an interior of an eco-friendly vehicle requiring high durability performance such as a hydrogen vehicle, an electric vehicle, and a hybrid vehicle using the same.

Example

The following examples illustrate the invention and are not intended to limit the invention.

Synthesis of hydroxyl terminated polyurethane prepolymer

[Synthesis Example 1]

70% by weight carbonate polyol (Ube Industries, Ltd., UH-200) with a number average molecular weight of 2,000, 26% by weight crystalline ester polyol derived from biomass (number average molecular weight 2,000, Songwon Chemical Co., Ltd. SS-236) and 4 wt% bio-1,3-propanediol (Susterra, DuPont Tate & Lyle Bio Products) were placed in a reactor and the resulting mixture was mixed homogeneously at 70°C to 80°C for 30 minutes. In consideration of the exothermic reaction, after cooling the reactor to about 65° C., 4.5 parts by weight of 4,4-diphenylmethane diisocyanate (MDI, trade name: Cosmonate, product manufactured by Kumho Mitsui Chemicals Corp) was added to the 100 parts by weight of the polyol mixture, and then the resulting mixture was reacted for about 3 hours to obtain a hydroxyl-terminated prepolymer-1 (with an OH group content of 2.67% by weight).

[Synthesis Example 2]

The polyol mixture was prepared under the same conditions as in Synthesis Example 1, and the reactor was cooled to a temperature of about 60°C to account for the exothermic reaction. After that, 3 parts by weight of 4,4-diphenylmethane diisocyanate (MDI, trade name: Cosmonate, a product manufactured by Kumho Mitsui Chemicals Corp) was added to 100 parts by weight of the polyol mixture, and then the resulting mixture was reacted for about 3 hours to obtain hydroxyl-terminated prepolymer-1 (OH group content of 2.9% by weight).

[Synthesis Example 3]

A hydroxyl-terminated prepolymer-3 (OH group content: 2.7% by weight) was obtained by reacting in the same manner as in Synthesis Example 1 except that the isocyanate was changed to dicyclohexylmethane diisocyanate (H ₁₂ MDI).

Preparation of Solvent-Free Polyurethane Adhesive Film

Example 1

100 parts by weight of the hydroxyl-terminated polyurethane prepolymer-1 in Synthesis Example 1 was heated and melted at 60°C, and then kept in a heat insulating container at 60°C. Subsequently, 26 parts by weight of an isocyanate-based compound (trade name: CosmonateLL, Kumho Mitsui Chemicals Corp., Modified MDI, NCO content of 28.5% by weight) and 0.5 parts by weight of a curing catalyst (Polycat-8, Air products) were mixed in a liquid The reaction mixture was obtained by stirring at a high speed of about 3,000 rpm in a high speed mixer for 2 seconds. The reaction mixture was coated and applied to release paper at a thickness of 250 μm, heated at a temperature of 110 to 135° C. for 3 minutes, and then dried. Then, the reaction mixture was cross-linked and cured, and then the release paper was left at about 70° C. for 24 hours to prepare a solvent-free bio-urethane adhesive film.

Example 2

Using the hydroxyl-terminated prepolymer-1 in Synthesis Example 1, under the same conditions as in Example 1, nitrogen as a non-reactive gas was injected into a high-speed mixer while stirring at a rate of 0.12 L/min to prepare A microporous solvent-free bio-polyurethane adhesive film is formed therein.

Example 3

A solvent-free bio-polyurethane adhesive film was prepared under the same conditions as in Example 1 using the hydroxyl-terminated prepolymer-2 in Synthesis Example 2.

Example 4

A solvent-free bio-polyurethane adhesive film was prepared under the same conditions as in Example 1 using the hydroxyl-terminated prepolymer-3 in Synthesis Example 3.

Example 5

The hydroxyl-terminated prepolymer-3 in Synthesis Example 3 was used, and the isocyanate-based compound was mixed with 18 parts by weight of hexamethylene diisocyanate (HDI) and 0.8 parts by weight of a curing catalyst (Polycat-8, Air products) The solution was mixed in a high speed stirrer at approximately 3,000 rpm for 2 seconds to obtain a reaction mixture. In the subsequent process, a solvent-free bio-polyurethane adhesive film was prepared under the same conditions as in Example 1.

Comparative Example 1

100 parts by weight of isocyanate group-terminated polyurethane prepolymer (PTMG-2000, HG/AA-2000, XDI type prepolymer, NCO content of 2.1% by weight) was heated and melted at 120°C, and 0.8 parts by weight of curing catalyst was added. (Polycat-8 parts by weight of colorant and 2 parts by weight of diluent) was stirred in a high-speed stirring molding machine at a high speed of 5,000 rpm for 2 seconds to obtain a reaction mixture. The reaction mixture was discharged onto release paper, and the coating thickness was 250 μm, and it was left to stand at room temperature in an atmosphere of 65% relative humidity for 72 hours to obtain an adhesive film.

Test Example

The present invention has been described in detail with reference to the exemplary embodiments of the present invention. It should be understood, however, that changes may be made to these exemplary embodiments by those skilled in the art without departing from the principles and spirit of the invention, the scope of which is to be defined in the appended claims and their equivalents.

Test Example 1: Measurement of Physical Properties of Solvent-Free Bio-Polyurethane Adhesive Films

Measurement of melt viscosity

The adhesive films in Examples 1 to 5 and Comparative Example 1 were observed at a given measurement temperature using a cone and plate viscometer.

Tensile properties

For the adhesive films in Examples 1 to 5 and Comparative Example 1, tensile properties were measured according to KS M 6782, ASTM D-412 and JISK7311.

Hydrolysis resistance

For the adhesive films in Examples 1 to 5 and Comparative Example 1, changes in appearance were observed after the hydrolysis resistance test under the experimental conditions of 110° C., 99% relative humidity and 48 hours.

peel strength

According to KS M 0533 and JIS K 6854, a hot melt cloth tape having a width of 25 mm was melted by heating on both side surfaces of the adhesive films in Examples 1 to 5 and Comparative Example 1 at 130° C. for 5 seconds to measure the interlaminar peel strength of the sheet.

Green carbon content

Green carbon content measurement method ASTM-D6866-12 (% bio-based carbon content) The biomass content of the adhesive films in Examples 1 to 5 and Comparative Example 1 was measured by radiocarbon analysis techniques.

[Table 1]

Note ¹⁾ Green carbon content is a value based on the weight of carbon.

From the results in Table 1, it was confirmed that in the case of Comparative Example 1, the isocyanate group-terminated urethane prepolymer containing an NCO content of 2.1% by weight was used, as a result, due to the large generation of air bubbles caused by moisture curing, The longer the aging time, the lower the peel strength. In addition, it was confirmed that the green carbon content was not detected due to the use of polyurethane prepared using petrochemical raw materials.

In contrast, in the cases of Examples 1 to 5, it was confirmed that, from the observation of an increase in the green carbon content relative to the total carbon amount, which is an indicator of reduction in greenhouse gas emissions, the use of biomass feedstocks was successful in treating artificial leather, while maintaining excellent physical properties including tensile strength, elongation and peel strength by using a solvent-free polyurethane adhesive film prepared from biomass-extracted polyester polyols, chain extenders, and the like.

The aging time of the prepared samples was observed. The aging time of the samples of Preparation Examples 1 to 5 was much faster than that of Comparative Example 1. It can be seen that the processing time is reduced due to the excellent cross-linking curability of the polyurethane binder and the excellent dimensional stability due to the fast curing rate.

Preparation of fibrous base layer

Example 6

According to a typical method for making dry nonwoven fabrics, 35 wt % of 2.5 denier and 51 mm fiber length composite spun fibers (composition: 50 wt % PET/50 wt % bio-PTT), 30 wt % of Typical nylon (PA) chopped fibers of 2 denier and fiber length of 51 mm, and 35% by weight of high shrinkage polyester (PET) chopped fibers of 1.4 denier and fiber length of 51 mm and heat shrink properties were mixed to make a nonwoven fabric net.

The carded mixed web and mixed fiber fleece ^were made and then needle punched at about 1200 perforations per square centimeter (PPSC) per cm, and the fibers were combined to produce a weight per unit area of about 240. to 250 g/m ² , a fibrous base layer composed of a non-woven layer with a thickness of about 1.0 mm and a green carbon (C ₁₄ ) content of 7% by weight.

Example 7

According to a typical method for the preparation of dry nonwoven fabrics, 45 wt % of a composite of 2.5 denier and a fiber length of 51 mm was spun into fibers (composition: 50 wt % PET/50 wt % bio-PTT), 30 wt % of Typical nylon (PA) chopped fibers of 2 denier and fiber length of 51 mm, and 25 wt % of high shrinkage polyester (PET) chopped fibers of 1.4 denier and fiber length of 51 mm and heat shrink properties were mixed to make a nonwoven fabric net.

Thereafter, the yarn obtained by twisting 17 strands of bio-PTT long fibers having 2.5 denier was used in a wire-free form to plain weave with a weaving density of 50 warps and 50 wefts per inch and a basis weight of 28 g ^The reinforcing fabric/m2 is bonded and introduced to the bottom of the nonwoven web, needle punched at about 1,300 perforations per square centimeter (PPSC)/ ^cm2 , and the fibers are combined to produce fibers comprising a composite nonwoven layer basal layer. The prepared fibrous base layer had a basis weight of about 240 to 250 g/m ² , a thickness of about 1.0 mm, and a green carbon (C ₁₄ ) content of 13 wt %.

Preparation of artificial leather products

Example 8

By combining bio-urethane resin (D-Ace-7000B, manufactured by Dongsung Chemical Co., Ltd), dimethylformamide (DMF), methyl ethyl ketone (MEK) and other additives (pigments and Thickener) The blended liquid prepared by mixing in proportions of 60 wt %, 5 wt %, 30 wt % and 5 wt %, respectively, was applied to a release paper at a thickness of 80 μm. The resulting release paper was immediately pre-dried at 80°C for 1 minute and then dried at 130°C for 3 minutes to form a bio-polyurethane skin surface layer film.

The reaction mixture prepared in Example 1 was coated and applied to a polyurethane skin surface layer film at a thickness of 250 μm, heated at a temperature of 110 to 135° C. for 3 minutes, and then dried. Then, the reaction mixture was cross-linked and cured, and then the release paper was left at about 70° C. for 24 hours to prepare a film of the solvent-free bio-urethane adhesive layer 200 .

Then, the biofiber base layer 300 prepared in Example 6 was laminated with a polyurethane adhesive layer, and the laminate was cured at about 70° C. for 24 hours, thereby manufacturing an eco-friendly artificial leather for automobile interiors product.

Example 9

An artificial leather product was produced in the same manner as in Example 8, except that the film of the solvent-free bio-urethane adhesive layer 200 in Example 2 was used.

Example 10

An artificial leather product was produced in the same manner as in Example 8, except that the film of the solvent-free bio-urethane adhesive layer 200 in Example 3 was used.

Example 11

An artificial leather product was produced in the same manner as in Example 8, except that the film of the solvent-free bio-urethane adhesive layer 200 in Example 3 was used.

Example 12

An artificial leather product was produced in the same manner as in Example 8, except that the biofiber base layer 300 prepared in Example 7 was laminated.

Comparative Example 2

100 parts by weight of isocyanate group-terminated polyurethane prepolymer (PTMG-2000, HG/AA-2000, XDI type prepolymer, NCO content of 2.1 wt%) was heated and melted at 12°C and kept at 120°C adiabatic In the tank, 12 parts by weight of PPG-5,000 (Kumho Petrochemical), 8 parts by weight of a colorant and 2 parts by weight of a diluent were stirred in a high-speed stirring molding machine at a high speed of 5,000 rpm for 3 seconds to obtain a reaction mixture. The prepared reaction mixture was discharged to a thickness of 150 μm on a release paper coated with a polyurethane resin and dried, then heated at a temperature gradient of 100 to 140° C. for about 3 minutes, and then dried. After that, the binder layer comprising the moisture-curable polyurethane hot melt resin is cross-linked and cured, and laminated with the fibrous base layer comprising the chopped fiber nonwoven fabric to manufacture artificial leather. Subsequently, the artificial leather was cured at 70° C. for 24 hours to obtain an artificial leather product for automobile interior.

Comparative Example 3

100 parts by weight of isocyanate group-terminated polyurethane prepolymer (NCO prepolymer/PTMG-2000, PPG-6000 (trifunctional group)-type prepolymer and NCO content of 12.5% by weight), 70.46 parts by weight of crosslinking agent ( PPG-2000/PPG-6000 (trifunctional group)/1,4-BG/catalyst, with a weight ratio of 70/15/15/0.06) and 2 wt. The reaction mixture was obtained through a separate line. After that, artificial leather was produced in the same manner as in Comparative Example 2.

Test Example 2: Measurement of Physical Properties of Artificial Leather Products

For the artificial leathers produced in Examples 8 to 12 and Comparative Examples 2 to 3, physical properties were measured in the same manner as in Test Example 1.

[Table 2]

From the results in Table 2, it was confirmed that when the polyurethane prepared by using petrochemical raw materials was applied in the case of Comparative Examples 2 and 3, the overall mechanical properties showed lower values than Examples 8 to 12. In addition, since the concentration of volatile organic compounds is very high, it can be seen that harmful components remain in the artificial leather due to the use of organic solvents.

In contrast, in the cases of Examples 8 to 12, it was confirmed that the overall physical properties including light resistance, rubbing colorability, and peel strength were excellent, and the concentration of volatile organic compounds was significantly reduced. In addition, since the green carbon content was 15% by weight or more, it was confirmed that biomass PU artificial leather was successfully processed using biomass raw materials.

For ease of explanation and precise definition of the appended claims, the terms "upper," "lower," "upper," "lower," "upper," "downward," "internal," "external," "internal," "outer", "inward", "outward", "inside", "outer", "front", "rear", "rear", "forward", "rear" are used with reference to the drawings The positions of these features are shown in the description to describe the features of the exemplary embodiments.

The foregoing descriptions of specific exemplary embodiments of the present invention have been presented for purposes of illustration and description. They are not exhaustive and do not limit the invention to the precise form disclosed, obviously many modifications and variations are possible in light of the above teachings. The exemplary embodiments were chosen and described in order to explain certain principles of the invention and their practical application, to thereby enable others skilled in the art to make and utilize various alternatives and modifications thereof. The scope of the invention is intended to be limited by the appended claims and their equivalents.

Claims (10)

1. Environmentally friendly artificial leather for automobile interiors, wherein a skin surface layer comprising bio-polyurethane; a solvent-free bio-polyurethane adhesive layer; and a biofiber base layer are stacked in this order, wherein the solvent-free bio-urethane adhesive layer comprises a hydroxyl-terminated polyurethane prepolymer prepared by polymerizing 2 to 5 parts by weight of an isocyanate-based compound with 100 parts by weight of a polyol mixture, the polyol mixture comprising: 1 ) carbonate polyols having a functionality of 2 or greater and a number average molecular weight of 500 to 3,000, 2) biomass-derived crystalline ester polyols having a curing temperature of 18°C to 55°C and a number average molecular weight of 1,000 to 3,000, and 3) biomass-derived chain extenders having a functionality of 3 or greater and a number average molecular weight of 50 to 500, wherein the green carbon _C14 content of the solvent-free bio-polyurethane adhesive layer is 15 to 35 wt%, and The biofiber base layer comprises a composite spun fiber comprising a polymer resin and a biomass-derived polytrimethylene terephthalate, wherein the polymer resin is selected from polyethylene terephthalate, polyacrylate, copolyethylene terephthalate, and polylactide, and the polymer resin is combined with biomass-derived polyethylene terephthalate Mix in a 1:1 weight ratio. 2. The eco-friendly artificial leather for automobile interiors according to claim 1, wherein the polyol mixture comprises 65 to 80 wt% carbonate polyol, 18 to 26 wt% crystalline ester polyol derived from biomass and 2 to 9 wt% chain extender. 3. The environment-friendly artificial leather for automobile interior according to claim 1, wherein the isocyanate-based compound is selected from the group consisting of hexamethylene diisocyanate HDI, isophorone diisocyanate IPDI, dicyclohexylmethane diisocyanate H ₁₂ One or more of MDI, xylylene diisocyanate XDI, and 4,4-diphenylmethane diisocyanate MDI. 4. The environment-friendly artificial leather for automobile interior according to claim 1, wherein the melt viscosity of the hydroxyl-terminated polyurethane prepolymer at 60° C. is 2,000 to 8,000 cPs, and the total amount of the hydroxyl-terminated polyurethane prepolymer is 2,000 to 8,000 cPs. It has a hydroxyl content of 1 to 3% by weight by weight. 5. The environment-friendly artificial leather for automobile interiors according to claim 1, wherein the solvent-free bio-urethane adhesive layer comprises 10 to 30 parts by weight of the isocyanate-based compound in 100 parts by weight of the hydroxyl-terminated polyurethane prepolymer and 0.01 to 5 parts by weight of a curing catalyst. 6. The eco-friendly artificial leather for automobile interiors according to claim 1, wherein the biomass-derived polytrimethylene terephthalate is formed by polycondensing biomass-derived 1,3-propylene glycol and terephthalic acid . 7. The eco-friendly artificial leather for automobile interior according to claim 1, wherein the biofiber base layer is composed of composite spun fibers comprising 30 to 50 wt%, nylon fibers of 25 to 35 wt%, and 25 to 35 wt% % by weight of a nonwoven layer of polyester fibers, or a composite nonwoven layer in which a reinforcing layer composed of biomass-derived polytrimethylene terephthalate is formed on the nonwoven layer. 8 . The environment-friendly artificial leather for automobile interior according to claim 1 , wherein the biofiber base layer has a unit area weight of 200 to 300 g/m ² and a green carbon C ₁₄ content of 1 to 20 wt %. 9 . 9. A method of manufacturing environmentally friendly artificial leather for use in automobile interiors, the method comprising: a) forming a bio-polyurethane skin surface layer on the release paper; b) forming a solvent-free bio-polyurethane adhesive layer by applying a solvent-free bio-polyurethane composition on the bio-polyurethane skin surface layer; and c) forming a biofiber base layer on the solvent-free biopolyurethane adhesive layer, wherein the solvent-free bio-urethane adhesive composition includes a hydroxyl-terminated polyurethane prepolymer prepared by polymerizing 2 to 5 parts by weight of an isocyanate-based compound with 100 parts by weight of a polyol mixture, the polyol mixture including 1 ) carbonate polyols having a functionality of 2 or greater and a number average molecular weight of 500 to 3,000, 2) biomass-derived crystalline ester polyols having a curing temperature of 18°C to 55°C and a number average molecular weight of 1,000 to 3,000, and 3) biomass-derived chain extenders having a functionality of 3 or greater and a number average molecular weight of 50 to 500, wherein the green carbon _C14 content of the solvent-free bio-urethane adhesive layer is 15 to 35 wt%, and The biofiber base layer comprises a composite spun fiber comprising a polymer resin and a biomass-derived polytrimethylene terephthalate, wherein the polymer resin is selected from polyethylene terephthalate, polyacrylate, copolyethylene terephthalate, and polylactide, and the polymer resin is combined with biomass-derived polyethylene terephthalate Mix in a 1:1 weight ratio. 10. The method of claim 9, wherein step b) further comprises preparing non-reactive nitrogen gas by injecting non-reactive nitrogen gas into a high-speed stirrer at a rate of 0.01 to 3 L/min. A microporous solvent-free bio-urethane adhesive layer is formed.

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